In this study, a laboratory-scale activated sludge reactor and a biotrickling filter were constructed to study the removal of methyl tert-butyl ether (MTBE) from air vented from contaminated sites. The activated sludge tank (0.4 m¡Ñ0.4 m cross-sectional area, 3.0 m height, and 480 L total volume) was made by acrylic resin. A mixed liquor suspended solids (MLSS) concentration of 2000-3000 mg/L was maintained in the experimental mixed liquor and the sludge was acclimated for 30 days under selected conditions of a Food to Microorganism Ratio (F/M) of 0.3 g BOD/(g MLSS¡Dday) and an influent gas MTBE concentration (C0) of 180 mg/Am3 (@27oC). Results on performance tests show that an average MTBE removal efficiency of 93.6% was obtained with the operation conditions of C0 of 610 mg/Am3 (@27oC), volumetric aeration rate of 0.063 m3/m3¡Dmin, MLSS of 2600 mg/L, and submerged liquid depth of 1.0 m. The biotrickling filter was made by combining two same type of acrylic resin columns (each 0.2 m inner diameter, 2.0 m height, and packed with 900 pieces of polypropylene Pall rings to a height of 1.35 m) in series for the test gas flow and in-parallel for the trickling liquid flow. Each test was operated for 8 hours to reach a steady state for a set of selected conditions (gas flow rate 0.050 m3/min and superficial gas velocity 0.027 m/s, trickling liquid flow rate 0.004 m3/min and pH: 6.8-7.2, and liquid/gas flow ratio: 80 L/m3). Results show that the MTBE removal efficiencies from the influent gas were 40%, 22% and 15%, respectively, with C0 of 50,100 and 230 mg/Am3 (@27oC).

Thesis (M.S.)--Worcester Polytechnic Institute. / Keywords: zeolite adsorption, TBA, tert butyl alcohol, wastewater remediation. Includes bibliographical references (leaves 60-62 ).

Thesis (Ph. D.)--Worcester Polytechnic Institute. / Keywords: Water; Adsorption; Molecular simulation; Nanoporous materials. Includes bibliographical references (p. 117-119).

Methyl tert-butyl ether (MTBE) has been used as a gasoline additive to improve the combustion efficiency and to replace lead since 1978. It is the most commonly used oxygenate now due to its low cost, convenience of transfer, and ease of blending and production. MTBE has become a prevalent groundwater contaminant because it is widely used and it has been disposed inappropriately. MTBE has been demonstrated an animal carcinogen. The US Environmental Protection Agency (US EPA) has temporarily classified MTBE as a possible human carcinogen and has set its advisory level for drinking water at 20-40 µg/L based on taste and odor concerns. The Taiwan Environmental Protection Administration (TEPA) also classifies it as the Class IV toxic chemical substances. Currently, natural attenuation (NA) as well as natural bioremediation or enhanced bioremediation are attractive remediation options for contaminated sites due to their economic benefit and environmental friendly. In general, in situ microorganisms at the contaminated site play a very important role in site restoration. Although early studies suggested that the biodegradability of MTBE was not significant, recent laboratory and field reports reveal that MTBE can be biodegraded under aerobic and anaerobic conditions. In addition, evidences and some successful cases of MTBE attenuation have been reported that make natural attenuation a considerable remedial strategy. However, the biodegrading rate might decrease if the nutritional and physiological requirements are not met. Thus, it is important to assess the biodegradability of natural microorganisms under various site conditions to obtain optimal remedial conditions. Contributions of intrinsic biodegradation and other abiotic mechanisms to the removal and control of contaminants should also be evaluated to provide sufficient information for remedial option determination. Moreover, isolation and identification of the dominant native microorganisms will be helpful to following remediation tasks. In the first part of this study, microcosm study and microbial identification technologies (denaturing gradient gel electrophoresis, DGGE) were applied to assess the biodegradability of MTBE by indigenous microbial consortia and to identify the dominant microorganisms at a MTBE-contaminated site (Site A). In the second part of this study, thorough field investigations were performed to evaluate the occurrence of natural attenuation of MTBE at two MTBE-contaminated sites (Site A and Site B). In addition, a natural attenuation model, BIOSCREEN, was performed to assess the effectiveness of natural attenuation on MTBE containment. The main objectives of this study contained the following: (1)Evaluate MTBE biodegradability under different redox conditions by the indigenous microorganisms. (2)Determine the dominant native microorganisms in MTBE biodegradation for further application. (3)Assess the feasibility of using natural attenuation to control the MTBE plume. (4)Evaluate the contributions of intrinsic biodegradation patterns on natural attenuation processes by BIOSCREEN. Results from the microcosm study reveal that MTBE could be biodegraded by aquifer sediments without the addition of extra carbon sources under aerobic conditions. The production of tert-butyl alcohol (TBA), a degradation byproduct of MTBE, was detected. Complete removal of TBA was also observed by the end of the experiment. Results from aerobic microcosms study indicate that oxygen might be the major limiting factor of MTBE biodegradation at Site A. Thus, MTBE at this site could be removed via natural biodegradation processes with the supplement of sufficient oxygen. Microcosm study with extracted supernatant of aquifer sediments as the inocula show that the indigenous microorganisms were capable of using MTBE as the sole carbon and energy source. The calculated MTBE degradation rate was 0.597 mg/g cells/h or 0.194 nmole/mg cells/h. No MTBE removal was observed under various anaerobic conditions. Results suggest that aerobic biodegradation was the dominant degradation process and aerobic bioremediation might be a more appropriate option for the site remediation. According to the results of DGGE analysis, aerobic MTBE-biodegrading bacteria, Pseudomonas sp. and Xanthomonas sp., might exist at this site. Although results of microcosm study show that MTBE could not be degraded under anaerobic conditions, the microbial identification indicates that some novel anaerobic microbes, which could degraded MTBE, might be present at this site. In addition, anaerobic microbes caused the consumption of electron acceptors (e.g., nitrate, ferric iron) and removal of benzene, toluene, ethylbenzene, xylenes (BTEX), 1,2,4-trimethyl benzene (1,2,4-TMB), and 1,3,5-trimethyl benzene (1,3,5-TMB) (TMBs) in the anaerobic microcosms. These results also indicate that the potential of anaerobes activities was high at Site A. Based on the results from the field investigation, natural attenuation of MTBE was occurring at both sites. MTBE plume at Site B could be effectively controlled via natural attenuation processes. Nevertheless, MTBE plume at Site A has migrated to a farther downgradient area and passed the boundary of the site. Field investigation results indicate that the natural attenuation mechanisms of MTBE at both sites were occurring with the first-order attenuation rates of 0.0021 and 0.0048 1/day at Sites A and B, respectively. According to BIOSCREEN simulation, biodegradation was responsible for 78% and 59% of MTBE mass reduction at Sites A and B, respectively. The intrinsic biodegradation had significant contributions on the control of MTBE plumes. Moreover, the dilution and dispersion processes might be the major mechanisms for the attenuation of MTBE in the downgradient areas. However, results also reveal that intrinsic biological processes might still fail to contain the plume if the selected point of compliance is not appropriate. Results of this study suggest that natural attenuation might be feasible to be used as a remedial option for the remediation of MTBE-contaminated site on the premise that (1) detailed site characterization has been conducted, and (2) the occurrence and effectiveness of natural attenuation processes have been confirmed. Based on the results from the field investigation and laboratory microcosm studies, MTBE could be biodegraded by natural microbial populations at the studied sites under both aerobic and anaerobic conditions and natural attenuation would be applied as a remedial option at MTBE-contaminated sites. Results from this study would be useful in determining the favorable bioremediation conditions and designing an efficient and cost-effective bioremediation system such as monitored natural attenuation (MNA) or in situ or on-site MTBE bioremediation system for field application.

Molecular simulations have become an important tool within the last few decades to understand physical processes in the microscale and customize processes in the macroscale according to the understanding developed at the molecular level. We present results from molecular simulations we performed to study the adsorption of hazardous organics in nanoporous materials. Adsorption of water in silicalite, a hydrophobic material, and the effect of defects were investigated by Monte Carlo simulations. Silanol nests were found to have a big impact on the hydrophobicity of silicalite. Even the presence of one silanol nest per unit cell caused a significant amount of water adsorption. We also investigated the effect of four different cations, H+, Li+, Na+, and Cs+. Their presence in silicalite increased the amount of water adsorbed. Monte Carlo and molecular dynamics simulations of MTBE adsorption in silicalite, mordenite, and zeolite beta with different Na+ cation loadings were carried out. The results revealed the importance of the pore structure on the adsorption of MTBE. Although these three zeolites have similar pore volumes, zeolite beta, with its pore structure which is mostly accessible to MTBE molecules, is predicted to adsorb significantly more MTBE than silicalite and mordenite. The Na+ cation loading, up to four cations does not have a significant effect on the adsorption capacity of the zeolites studied here, however, for silicalite and zeolite beta increasing the Na+ content increases the amount adsorbed at very low pressures. A new force field was developed by Monte Carlo simulations for 1,4-Dioxane, an important industrial solvent which has emerged as a potentially significant threat to human health. The objective was to develop reliable atom-atom interaction parameters to use in the simulations of the adsorption of 1,4-Dioxane in different adsorbent materials. Predictions of critical point data, liquid and vapour densities, heats of vaporization with our new force field were in good agreement with experimental data and outperformed predictions from simulations with other force field parameters available in literature. To obtain the isotherms of MTBE and 1,4-Dioxane adsorption from water in silicalite Monte Carlo simulations were performed. First we optimized the interaction parameters between the atoms of silicalite and the atoms of MTBE and 1,4-Dioxane. Using these optimized parameters we simulated the adsorption of MTBE and 1,4-Dioxane from water in silicalite. Despite the agreement of simulated and experimental isotherms of pure components, simulated isotherms of MTBE and 1,4-Dioxane adsorption from water in silicalite did not yield satisfactory results. Monte Carlo simulations were performed to investigate the affinity between two hazardous materials, PFOA and 1,1-DCE; and four different zeolites. Binding energies and Henry's constants were computed. For both PFOA and 1,1-DCE zeolite-beta had the highest affinity. The affinity between activated carbon with polar surface groups and water, and 1,4-Dioxane were investigated to shed light on why activated carbon is ineffective to remove 1,4-Dioxane from water. Results showed that presence of polar surface groups increased the affinity between water and activated carbon, while the affinity between 1,4-Dioxane and activated carbon was not effected by the presence of polar surface groups.

L’éthyl tert-butyl éther (ETBE) et le méthyl tert-butyl éther (MTBE) sont des éthers carburants utilisés comme additifs dans les essences sans plomb. Du fait de leur utilisation massive, de nombreux cas de pollutions d’aquifères ont été répertoriés, en particulier pour le MTBE, et ces composés représentent donc un risque sanitaire potentiel. Des travaux récents ont permis de mettre en évidence différents micro-organismes capables de dégrader ces composés malgré leur faible biodégradabilité dans l'environnement. Néanmoins, une meilleure compréhension de l'écologie et de la régulation de ces capacités de dégradation permettrait une meilleure gestion de la bioremédiation de sites contaminés par l'ETBE ou le MTBE.L’objectif de la thèse, réalisée dans le cadre d'un projet ANR Blanc (MiOxyFun), est de mieux comprendre l'écologie des communautés microbiennes impliquées dans la dégradation de ces éthers et leur relation avec la régulation ainsi qu'avec les cinétiques de dégradation de ces composés par des membres spécifiques de ces communautés. Ainsi, à partir de différents échantillons environnementaux venant de sites pollués par l'ETBE ou le MTBE, des enrichissements ont pu être réalisés en laboratoire afin d'étudier leurs microflores. Ces enrichissements ont été étudiés notamment pour leurs cinétiques de dégradation, la composition de leurs communautés bactériennes, et pour l'isolement de souches bactériennes directement impliquées dans la dégradation de ces composés. L'étude des cinétiques de dégradation de l'ETBE ou du MTBE par différents enrichissements obtenus sur ETBE (cinq) et sur MTBE (six) a permis de montrer des profils de dégradation très différents. La dégradation était généralement lente et s'accompagnait d'un faible rendement en biomasse avec parfois accumulation transitoire de tert-butanol (TBA). Les capacités de dégradation d'autres composés des essences (BTEXs et n-alcanes) étaient aussi différentes d'un enrichissement à l'autre, le benzène, entre autres, étant dégradé par 10/11 enrichissements. Des techniques d'empreinte moléculaire (RISA, DGGE) ont permis de constater que les communautés bactériennes présentes dans les cinq enrichissements sur ETBE étaient différentes de celles sur les enrichissements sur MTBE. Les enrichissements sur ETBE ont fait spécifiquement l'objet d'une étude par analyse de banques de clones réalisées à partir des gènes codant l'ARNr 16S de ces enrichissements. Cette étude a montré la prédominance des Proteobacteria dans trois enrichissements, la prédominance des Acidobacteria dans un autre ainsi qu'une composition plus héterogène dans le cinquième. De plus, des Actinobacteria ont été détectées dans les 5 enrichissements.En parallèle, plusieurs souches possédant des capacités de dégradation ont été isolées des enrichissements: Rhodococcus sp. IFP 2040, IFP 2041, IFP 2042, IFP 2043 (dégradant l'ETBE jusqu'au TBA), une Betaproteobacteria IFP 2047 (dégradant l'ETBE), Bradyrhizobium sp. IFP 2049 (dégradant le TBA), Pseudonocardia sp. IFP 2050 (dégradant l'ETBE et le MTBE), Pseudoxanthomonas sp. IFP 2051 et une Proteobacteria IFP 2052 (dégradant le MTBE). Une étude par qPCR sur les gènes codant l'ARNr 16S a montré la prédominance de certaines souches isolées dans les enrichissements ETBE. Enfin, plusieurs gènes connus comme étant impliqués dans la dégradation des éthers carburants ont pu être mis en évidence dans les enrichissements et dans certaines des souches isolées. / ETBE and MTBE are fuel oxygenates added to unleaded gasoline to improve combustion. Due to their extensive use, numerous aquifers have been contaminated, particularly by MTBE. The use of ETBE and MTBE is considered to represent an environmental risk. Recent research has uncovered a range of microorganisms capable of degrading these compounds, even though their environmental half-lives are long. Improved understanding of the ecology and regulation of this degradative ability could improve the management of the ETBE and MTBE contaminated site remediation. The aim of this work, taking place in the framework of the ANR project MiOxyFun was to investigate the ecology of ETBE- and MTBE-degrading microbial communities and their relationship to the regulation and kinetics of ETBE- and MTBE-degradation by specific members of these communities. Several ETBE- and MTBE-degrading microbial communities were enriched in the laboratory from environmental samples from contaminated sites throughout the world. These enrichments were examined for their degradation kinetics, microbial community structure, and used to isolate specific community members actively degrading ETBE and/or MTBE. The ETBE or MTBE biodegradation kinetics of the five ETBE- and six MTBE- degrading enrichments demonstrated a diversity of biodegradation rates. Overall, biodegradation was generally slow and associated to a low biomass yield. Tert-butanol (TBA) was transiently produced in several cases. Biodegradation of other gasoline compounds (BTEXs and n-alkanes) was tested and varied among the enrichments studied. Benzene, however, was degraded in 10 out of the 11 enrichments. DNA fingerprinting techniques (RISA, DGGE) showed that the microflora present in the five ETBE enrichments were different from those of the MTBE enrichments. The ETBE enrichments were studied further by sequencing the 16S rRNA genes extracted, amplified and cloned from these enrichments. Proteobacteria dominated three of the ETBE enrichments, Acidobacteria in another one, and a more heterogeneous composition was found in the fifth ETBE enrichment. Actinobacteria were detected in all five enrichments. Several strains with ETBE or MTBE degradation capacities were isolated: Rhodococcus sp. IFP 2040, IFP 2041, IFP 2042, IFP 2043 (degrading ETBE to TBA),a Betaproteobacteria IFP 2047 (degrading ETBE), Bradyrhizobium sp. IFP 2047 (degrading TBA), Pseudonocardia sp. IFP 2050 (degrading ETBE and MTBE), Pseudoxanthomonas sp. IFP 2051 and a Proteobacteria IFP 2052 (degrading MTBE). Quantification of the 16S rRNA gene confirmed the relatively high number of these isolates in some of the ETBE enrichments. Several genes involved in ETBE and/or MTBE biodegradation were detected in some of the enrichments and in some of the isolated strains.